Abstract
Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.
| Original language | English |
|---|---|
| Pages (from-to) | 3493-3500 |
| Number of pages | 8 |
| Journal | European Journal of Inorganic Chemistry |
| Issue number | 22 |
| DOIs | |
| Publication status | Published - Aug 2008 |
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Keywords
- CH activation
- Deuteration
- DFT calculations
- H/D exchange
- Ruthenium dihydrogen complexes
ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Ruthenium dihydrogen complex for C-H activation : Catalytic H/D exchange under mild conditions. / Prechtl, Martin H G; Hölscher, Markus; Ben-David, Yehoshoa; Theyssen, Nils; Milstein, David; Leitner, Walter.
In: European Journal of Inorganic Chemistry, No. 22, 08.2008, p. 3493-3500.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ruthenium dihydrogen complex for C-H activation
T2 - Catalytic H/D exchange under mild conditions
AU - Prechtl, Martin H G
AU - Hölscher, Markus
AU - Ben-David, Yehoshoa
AU - Theyssen, Nils
AU - Milstein, David
AU - Leitner, Walter
PY - 2008/8
Y1 - 2008/8
N2 - Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.
AB - Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.
KW - CH activation
KW - Deuteration
KW - DFT calculations
KW - H/D exchange
KW - Ruthenium dihydrogen complexes
UR - http://www.scopus.com/inward/record.url?scp=53249149348&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=53249149348&partnerID=8YFLogxK
U2 - 10.1002/ejic.200800359
DO - 10.1002/ejic.200800359
M3 - Article
AN - SCOPUS:53249149348
SP - 3493
EP - 3500
JO - Chemische Berichte
JF - Chemische Berichte
SN - 0009-2940
IS - 22
ER -